Toilet bars

ABSTRACT

A TOILET BAR CONSISTING ESSENTIALLY OF A MIXTURE OF C10-20 STRAIGHT: SULPHONATES, THE WEIGHT RATIO OF ALKANE SULPHONATE TO ALKENE SULPHONATE BEING BETWEEN 4:1 AND 2:3. PREFERABLY THE ALKANE SULPHONATE CONTAINS AT LEAST 75% BY WEIGHT OF C10-16 MATERIAL AND THE ALKANE SULPHONATE CONSISTS PREDOMINANTLY OF C14-18 MATERIAL.

United States Patent 3,812,060 TOILET BARS Allan Alsbury, Wirral, England, assignor to Lever Brothers Company, New York, N.Y.

No Drawing. Continuation of application Ser. No. 84,485, Oct. 27, 1970, which is a continuation of application Ser. No. 868,656, Oct. 22, 1969, which in turn is a continuation of application Ser. No. 618,333, Feb. 24, 1967, all now abandoned. This application Jan. 12, 1972, Ser. No. 217,221

Int. Cl. Clld N14 US. Cl. 252-555 3 Claims ABSTRACT OF THE DISCLOSURE A toilet bar cosisting essentially of a mixture of C1040 straight-chain primary alkane sulphonate and C alkene sulphonate, the weight ratio of alkane sulphonate to alkene sulphonate being between 4:1 and 2:3. Preferably the alkane sulphonate contains at least 75% by weight of C1046 material and the alkene sulphonate consists predominantly of C material.

This is a continuation of application Ser. No. 84,485, filed Oct. 27, 1970, which is a continuation of application Ser. No. 868,656, filed Oct. 22, 1969, which in turn is a continuation of application Ser. No. 618,333, filed Feb. 24, 1967, all of which are now abandoned.

The present inventoin relates to toilet bars based on nonsoap detergents.

It has been proposed that such bars should be based on straight-chain primary alkane sulphonates and the use of C1540 straight-chain primary alkane sulphonates has been particularly advocated.

It has been found that the lathering performance of bars based on such alkane sulphonates can be improved, particularly in respect of the quickness with which lather develops, by admixing alkene sulphonate with the alkane sulphonate and that synergistic foaming occurs in such mixtures.

A further advantage of the addition of alkene sulphonate is that the mixture is more easily milled and plodded than alkane sulphonate alone; further, the bar has better cohesion than one based on alkane sulphonate alone.

The alkane sulphonates of the invention can be made by free radical (e.g. peroxide) catalyzed addition of sodium or other alkali-metal bisulphite to alpha-olefins.

The alkene suphonates are those compounds obtained by the reaction of sulphur trioxide with alpha-olefins and subsequent neutralization and hydrolysis. The composition of the resulting mixture is not precisely known; it consists largely of hydroxy alkane l-sulphonate and true alkene 1- sulphonate and for convenience is hereafter referred to simply as alkene sulphonate.

The invention provides a toilet bar consisting essentially of a mixture of C1040 straight-chain primary alkane sulphonate and C alkene sulphonate, the weight ratio of alkane sulphonate to alkene sulphonate being between 4:1 and 2:3. It is preferred that the alkane sulphonate should contain at least 75% by weight of C1046 material. It is further preferred that the alkene sulphonate should consist predominantly of C1448 material.

As commercially supplied, alpha-olefins are generally available not as single substances but as mixtures of cuts of a particular range of hydrocarbon chain lengths. In the 3,812,060 Patented May 21., 1974 "ice present invention the following cuts have been found particularly suitable for preparation of the alkane and alkene sulphonates:

(a) from cracked waxes: C ;C C1840 (b) from Ziegler process: C C C However, the use of other cuts" within the general ranges given previously is included within the scope of the invention.

Toilet bars according to the invention have been found to be surprisingly mild, particularly in respect of bars containing a high proportion of shorter chain alkane sulphonate, in relation to their effect on skin and this property together with their exceptional lathering performance makes them especially suited for personal washing purposes.

The use of other active ingredients, such as soap, in significant amounts, such as up to 25% by weight of the bar is not excluded.

The water content of the bar can vary from 2 to 20%, preferably from 5-15 by weight of the finished product.

The cationic component in the bars of the invention can be any suitable alkali-metal or alkaline earth metal cation or mixture of these.

If desired, inorganic salts can be included for the purposes for which they are normally employed in toilet bars, it being understood that some inorganic salts such as sodium sulphate are not recommended because of their adverse effect on the user properties of the bar such as appearance and feel. Other ingredients likewise conventionally employed in toilet bars can be included such as superfatting agents and/or lather modifiers, coloring agents, pigments, bactericides, fungicides, preservatives, perfumes, sequestering agents and the like.

.Desirably the tablets will be neutral in reaction but if desired their reaction may be modified by the addition of suitable acids (e.g. lactic acid, phosphoric acid) or alkalies (e.g. sodium carbonate) so that the solution resulting from the tablet has any desired pH between 3 and 10 /2.

The toilet bar of the invention can be prepared by conventional techniques. For example, the dry ingredient in powder form or flake form (the flake containing 3-4% moisture) can be milled together with the water needed for the final composition to form a flake which is then plodded and stamped. Alternatively the neutralized sulphonated material can be mixed together, dried conventionally and further processed as above.

The active ingredients normally employed in detergent compositions can be used in small amounts in the toilet bar of the invention without afiecting the synergistic lathering properties adversely. Examples of suitable anionic and nonionic active ingredient follow. Preferred are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionate; acyl N-methyl taurides; alkylbenzenesulfonates; alkyl phenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain 10 to 20 carbon atoms. They are used in the form of water soluble salts, the sodium,

potassium, ammonium and alkylol-ammonium salt, for example. Specific examples are: sodium lauryl sulfate; potassium N-methyl lauroyl tauride; triethanolammonium dodecylbenzene-sulfonate.

The examples of nonionic organic detergents are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms (e.g. octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkyl phenol in the range of :1 to :1 condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products range of from 5000 to 11,000; the condensation product of from about 5 to moles of ethylene oxide with one mole of a straight or branched chain aliphatic aloc'hol containing from 8 to 18 carbon atoms (e.g. lauryl alcohol).

Alkali metal salts, such as sodium and potassium salts, of the supplementary detergent are suitable and if alkanolammonium cations (e.g. ethanolammonium, diethanolammonium, and triethanolammonium) are to be introduced, it is often convenient to do so by means of an alkanolammonium salt of the supplementary detergent.

It has been found advantageous in some instances to include higher molecular weight polymeric substances of natural or synthetic origin in the toilet bar of the invention. Suitable additives of this type include starch, starch lower alkyl ethers, starch lower alkyloxy ethers, starch lower alkyl carboxy ethers, starch lower alkylsulphonate ethers, and the like, cellulose lower alkyl ethers, cellulose lower alkyloxy ethers, cellulose lower carboxy ethers, cellulose lower alkyl sulphonate ethers, sulphated high molecular carbohydrates of the type of slippery elm mucilage, chondroitin sulphate, and the like; polyamides such as proteins, polypeptides, polyacrylamides and the like; polyalkylene oxides particularly polyethylene oxides, e.g. carbowaxes, polyoxes (RTM) and the like; very high molecular weight water-soluble polymers and copolymers of vinyl alcohol, maleic acid, acrylic acid, itaconic acid, pyrrolidone, allyl alcohol, and the like, a proportion of the polymerized monomer units carrying a carboxy, sulphate, sulphonate, phosphate or phosphonate ionizing group and the like.

The invention is further illustrated by the following examples:

EXAMPLE 1 The synergistic improvement in lather volume generated in washing with tablets according to the present invention is shown by this test, designed to simulate normal hand washing.

Lather volume test The tablet is conditioned by use in normal washing once or twice to produce an in-use rather than fresh surface. This ensures that the surface is the same at the beginning as at the end of the test.

The operator uses 2% litres of water at the desired temperature (usually 20 C. or C.) in a hand bowl. Surgical quality rubber gloves are worn to obviate the variable effects of sebum from the skin, without destroying the sensitivity of the operation. The gloved hands and the tablet are dipped into the water, removed and the tablet twisted 15- times in the hands as in normal washing, then placed on a drained dish. The hands are rubbed together, palm to palm 10 times, then each hand twisted in the other, alternately 10 times. The rubbing and twisting sequence is repeated and the lather so formed collected in a measuring cylinder.

The sequence of operations from the 15 twists of the tablet is repeated twice more and the total volume of lather from the three latherings measured.

Tests are performed, desirably in duplicate.

The tablets used in the following tests were made from 0 and C1540 alkane and C1540 alkene sulphonates.

The alkane sulphonates were made by peroxide-initiated free radical addition of bisulphite; the alkene sulphonates by reacting alkene with 50 air in a falling film reactor. The lather volumes obtained are shown on the following table.

RESULTS OF DATHER VOLUME TESTS AT 20 AND 40 C.

Proportions by weight of alkanealkene sulphonate in the tablet Alkane sulphonate Lather volume Tablet Alkene Reference No. il-ll Cit-2 sulphonate 20 C. 409 C.

1 Control 410 475 2 Control.-. 100 290 3 Control 100 380 550 4 80 565 690 70 675 825 60 675 835 40 525 665 540 550 30 325 310 50 360 360 70 300 345 20 540 545 20 575 615 33% 700 625 50 690 675 70 500 600 From the above figures it can readily be seen that addition of C1540 alkene sulphonate to either C1145 or C1540 alkane sulphonate causes marked increase in lather voltime over that expected from the control figures.

EXAMPLE 2 This example illustrates the synergistic improvement in the speed of lathering obtained by the use of mixtures of alkene alkane sulphonate and alkane sulphonate according to the invention. The following speed of lathering test was employed:

Speed of lathering test The tablet is conditioned by use in normal washing once or twice to produce an in-use rather than fresh surface. This ensures that the surface is the same at the beginning as at the end of the test.

The operator uses 2% litres of 24-26 H. water at the desired test temperature (usually 20 C. or 40 C.) in a hand bowl. The conditioned tablet and hands are dipped into water, withdrawn, and the tablet twisted once in the hands as in normal washing. The tablet is placed on a drained dish, the hands rubbed together twenty times and then rinsed in the water. The rinsing is carried out in a standard manner with a fixed amount of agitation of the water. This process is repeated with 1, 2, 2, 5, 5, 10 and 10 twists until a lather is first produced on the surface of the water.

RESULTS OF "SPEED OF LATHERING TEST" AT 20 C.

Alkane Alkene Twists to lather at 20 C. Table Reference sulphonate sulpho- No. (as in nate Lather height Example 1) 0 -15 015-20 01 Twists and stability 1 Control.-- 35+ No lather. 2 Control.-- 15 fairly stable. 3 Contr 2 Do. 10 (Control) 50 35+ No lather. 11 (Control) 70 10 1 unstable. 9 (Control) 30 5 mod. stable, collapse to M, 60 40 2 1" very stable. 20 2 l stable.

20 60 1 1% very stable. 60 20 2 1" very stable. 40 60 2 1% very stable.

EXAMPLE 3 A preferred embodiment of the invention is a tablet consisting essentially of:

Component: Percent by weight C1145 alkane sulphonate 50 C154 alkane sulphonate 10 C alkene sulphonate (the material being prepared from cracked wax alpha-olefin) 40 EXAMPLE 4 Another preferred embodiment of the invention is a tablet consisting essentially of:

C1448 Ziegler alkene sulphonate (that is, the sulphonate was prepared from alpha-olefin produced by the Ziegler process) 40 In Examples 3 and 4 12-14% of water was incorporated in the mixture during processing so that the bar was finished to a nominal water content.

In the above examples in all cases the cation is sodium.

What is claimed is:

1. A toilet bar consisting essentially of a mixture of C1040 straight-chain primary alkane sulphonate and C1444 alkene sulphonate, the cation being an alkali metal, an alkaline earth metal or a mixture of these, the weight ratio of alkane sulphonate to alkene sulphonate being between 4:1 and 2:3.

2. A toilet bar according to claim 1 wherein the alkane sulphonate contains at least by weight of C1046 material.

3. A toilet bar according to claim 1 or claim 2 wherein the alkene sulphonate consists predominately of C1448 material.

References Cited UNITED STATES PATENTS 1,906,484 5/1933 Nuesslein 252-421 3,186,948 6/1965 Sweeney 252552 3,346,629 10/ 196-7 Broussalian 260513 3,409,637 11/1968 Eccles et a1. 260-327 3,332,874 7/1967 Coward et a1. 252-555 X LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 252554 UNITED STATES PATENT OFFICE QERTIFICATE ()F CORRECTION Paten N 3 .812 .060 Dated Max) 21. v 1974 lnventofls) Allan Alsburv It iscertified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 10, after"Ser. No. 217,221", add the following: ---Claims priority applicationGreat Britain, February 25, 1966, 8532/6 6-.

Signed and sealed this 3rd day of Decem ber, 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR; c. MARSHALL ,DANN Attes'cing Officer I I Commissioner of Patents FORM 9 v I uscoMM-Dc soars-P69 l A U.S. GOVERNMENT PRlNTlNG OFFICE: 959 0-356-33 

